JPH0112742B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel intermediate compound for producing a novel cyclopropane derivative useful as an insecticide and acaricide, and a method for producing the same. Although it has been known for many years that certain naturally occurring cyclopropane carboxylic acid esters have insecticidal properties, such esters are very easily degraded by ultraviolet light and are therefore not very useful in the agricultural field. Therefore, in an attempt to find compounds with sufficient photostability for use as general agricultural insecticides, several synthetic compounds based on cyclopropanecarboxylic acid (e.g., as described in British Patent Nos. 1,243,858 and 1,413,491) have been developed. Compounds described) have been evaluated. The present inventor has now proposed the following formula: [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or radical

[Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine), and R ³ represents hydrogen, cyano or ethynyl]
We have discovered that the cyclopropane derivative represented by the above formula has extremely excellent insecticidal and acaricidal activity and good resistance to photodegradation, and we have also created a compound useful as a raw material or intermediate for the production of the useful cyclopropane derivative of the above formula. did. Therefore, the present invention provides the following formula: [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or radical

[Formula] (wherein X, Y and Z each represent hydrogen, fluorine or chlorine) and Q represents a hydroxy group, a lower alkoxy group containing up to 6 carbon atoms or a chlorine atom] Propane derivatives are provided. A preferred group of intermediate compounds is of the formula
One of R ¹ and R ² represents a group WCF ₂ − (W has the meaning above), and the other represents a group

[Formula] (X, Y and Z have the above meanings), and Q
is a compound representing hydroxy, lower alkoxy having 1 to 3 carbon atoms, and chlorine. Among other things, R ¹
Particularly preferred are compounds in which R 2 and R ² are both trifluoromethyl. Another preferred group of intermediate compounds is one of the formulas in which one of R ¹ and R ² represents the radical WCF ₂ -, where W is hydrogen, fluorine or chlorine, and the other represents fluorine, chlorine or bromine; A compound in which Q represents hydroxy, lower alkoxy having 1 to 3 carbon atoms, or chlorine. Particularly preferred are compounds in which one of R ¹ and R ² represents trifluoromethyl and the other represents chlorine or bromine. The compounds represented by the formula may exist in various geometric and stereoisomeric forms. For example, cis and trans isomers resulting from the type of substitution on the cyclopropane ring and E- and Z-isomers resulting from substituted vinyl groups when R ¹ is different from R ² may exist. Furthermore, 2 of the three carbon atoms of cyclopropane
are asymmetrically substituted, so R configuration or S
It can exist by arrangement. Examples of specific intermediate compounds according to the invention include those represented by the formula; In the above formula, R ¹ and R ² are preferred in the formula
Having the specific meanings given above as R ¹ and R ² , Q represents chlorine, hydroxy or ethoxy. The method for producing the compound of the formula according to the present invention will be explained below. A compound in which Q is hydroxy is
It is obtained by hydrolysis of compounds of the formula in which Q is lower alkoxy, which can be converted into compounds of the formula in which each Q is chlorine, for example by reaction with thionyl chloride. All compounds of the formula
As described below, it can be used directly or indirectly in the production of esters of the above formula having insecticidal activity (hereinafter referred to as insecticidal ester compounds or final ester compounds). Compounds of the formula in which Q is lower alkoxy, i.e. the following formula: [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or radical

The compound represented by the formula [wherein X, Y and Z represent hydrogen, fluorine or chlorine, respectively] and Q ¹ represents a lower alkoxy group containing up to 6 carbon atoms] can be prepared by various methods. Can be manufactured. One method is as follows: diene compound with a lower alkyl ester of diazoacetic acid. This method allows for the direct production of the required compounds of formula. This is conveniently carried out using an excess of diene as solvent for the alkyl diazoacetate in the presence of a metal catalyst, such as copper or bronze powder. According to a variant of the above method, a compound of the formula " The compound represented by can be converted. (In the formula, R ¹ ' and R ² ' are both trifluoromethyl groups, or one of R ¹ ' and R ² ' is a trifluoromethyl group and the other is a difluoromethyl group, and Q ¹ is 6 an example of a chemical dehydrating agent is phosphorus pentoxide. A compound of the formula: is obtained by reacting a ketone with 3-methylbutene-1, preferably under pressure. Corresponding compounds of formula are obtained by dehydrating compounds of formula, for example with phosphorus pentoxide. Compounds in which R ¹ and R ² are both haloalkyl or one is haloalkyl and the other is methyl also have the formula: The corresponding ketone is obtained by treatment of a 3,3-dimethylallyltriphenylphosphonium halide (preferably chloride or bromide) with a suitable dehydrohalogenating agent, e.g. an alkyllithium compound such as n-butyllithium. It can be produced by reacting with ylide.
Phosphonium halide is obtained by the reaction of triphenylphosphine and 3,3-dimethylallyl halide. The dienes obtained by this method include those in which R ¹ and R ² are as shown in the table below: R ¹ R ² CF ₃ CF _{3 CHF 2} CHF ² CF ₃ CHF ₂ CF ₃ CH _{3 CF 2 Cl} Examples of compounds of the formula CF ₂ Cl CHF ₂ CF ₂ Cl are 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhexene-2 and 5-hydroxy-2-
methyl-6,6-difluoro-5-trifluoromethylhexene-2, which upon dehydration form 2-methyl-6,6,6, an example of a compound of formula
-Trifluoro-5-trifluoromethylhexadiene-2,4 and 2-methyl-6,6-difluoro-5-trifluoromethylhexadiene-
It can be 2 or 4. Another method for producing the compound of the present invention represented by the above formula ' is the following formula: (In the formula, R ¹ , R ² and Q ¹ have the above-mentioned meanings, and W′ and W″ each represent fluorine, chlorine or bromine,
(provided that when R ² is bromine, W' represents bromine) is treated with at least 2 moles of base. Suitable bases for carrying out this process are tertiary amines such as pyridine, triethylamine, diethylaniline and N-methylpiperidine and alkali metal lower alkoxides (having up to 6 carbon atoms) such as sodium methoxide, sodium ethoxy sodium t-butoxide and potassium t-butoxide
Butoxide. The process is conveniently carried out in a diluent or solvent of the reactants and base used. A particularly convenient way of carrying out this process is to prepare a solution of a compound of the formula dissolved in an alcohol corresponding to the alkali metal alkoxide used.
It is to be processed for 20 hours. At least 2 moles of base are required to convert a compound of formula to a compound of formula ', and the process involves two steps: cyclization and β-elimination of the hydrogen halide, but these two steps are It is unclear in what order they will occur or if they will occur simultaneously. If this process is carried out using only one molar equivalent of base, three different products are obtained. (wherein R ¹ , R ² , W′, W″ and Q ¹ each have the meaning given above.) Further treatment of each of these three products with 1 molar equivalent of base yields a compound of formula ′. Compounds of formula useful as intermediates in the preparation of compounds of formula ' are obtained by formula: (wherein Q ¹ has the meaning given above) and the following formula: (wherein R ¹ , R ² , W′ and W″ have the meanings given above) in the presence of a free radical initiator. It can be a physical initiator, such as irradiation with a light source (e.g. an ultraviolet source), or a conventional chemical free radical catalyst, such as benzoyl peroxide or azobisisobutyronitrile. It is expedient to carry out the reaction using minutes, at a temperature of 50 to 150°C, preferably 80 to 120°C, optionally in a closed vessel under the autogenous pressure of the reaction, for 1 to 20 hours.Particularly useful compounds of the formula 3,3-dimethyl-
Ethyl 4-pentenoate, but other lower alkyl esters may also be used. 3,3-dimethyl-4- represented by the formula
Instead of esters of pentenoic acid it is also possible to use other compounds whose carboxylate functions are replaced by other equivalent functions. By "equivalent functional group" is meant here a functional group, such as a nitrile, acetyl or formyl group, which can subsequently be converted chemically by oxidation or hydrolysis into a carboxylic acid group without disturbing the above-mentioned process. Alternatively, instead of the compound of formula: (wherein Q' is alkoxycarbonyl, cyano or acetyl and Q'' is cyano or alkoxycarbonyl) can be used. Yet another method by which compounds of formula ' can be prepared is by
Reacting a diene of the formula with an alkyl malonate in the presence of a reducing copper salt and optionally another salt selected from the halides of metals of Groups and Groups of the Periodic Table, such as lithium chloride or calcium chloride. This includes the step of causing The following equation is obtained: The initial product having the formula (R ¹ , R ² , Q ¹ and Q″ have the meanings given above) can be converted into the desired product of formula ′ by conventional hydrolysis and esterification. Examples of compounds of the formula useful in the above method are hexafluoroethane, chloropentafluoroethane,
1,1-dichlorotetrafluoroethane, 1,2
-dichlorotetrafluoroethane, 1,1,1-
Trichlorotrifluoroethane, 1,1,2-trichlorotrifluoroethane, 1,1,1-tribromotrifluoroethane, 1,1,1,3-tetrachlorotetrafluoropropane and 1,1,
3-Trichloropentafluoropropane. When carrying out various methods of preparing intermediates of the formula, the products usually result in mixtures of various geometric isomers. For example, mixtures of cis and trans isomers (often with a preference for monoisomers) may be obtained;
If R ¹ is different from R ² , both the cis and trans Z- and E-isomers (again, the -isomer often prevails) are obtained. If these isomers are not separated by physical methods, such as fractional crystallization of the carboxylic acid, the final ester compound will also consist of a mixture of various isomers containing two or more compounds. The final target insecticidal ester compound can be prepared starting from a compound of the formula according to the invention by conventional esterification methods as described below. (a) The following formula: The acid of is given by the following formula: can be directly reacted with alcohol.
This reaction is preferably carried out in the presence of an acid catalyst, such as dry hydrogen chloride. (b) The following formula: The acid chloride of is expressed as: can be reacted with alcohol. This reaction is preferably carried out in the presence of a base, such as pyridine, an alkali metal hydroxide, carbonate or alkoxide. Alternatively, when R ³ is a cyano group, a mixture of an alkali metal cyanide and 3-phenoxybenzaldehyde can be used instead of α-cyano-3-phenoxybenzyl alcohol. (c) The following formula: or preferably its alkali metal salt, of the following formula: (wherein Q′ is halogen, preferably chlorine) or such a halide and a tertiary
amines such as pyridine or trialkylamines such as triethylamine. (d) The following formula: (In the formula, R ⁴ is lower alkyl having 6 or less carbon atoms,
The lower alkyl ester (preferably methyl or ethyl) of The transesterification reaction is carried out by heating with alcohol. The method preferably uses a suitable catalyst,
For example, it is carried out in the presence of an alkali metal alkoxide such as sodium methoxide or an alkylated titanium derivative such as tetramethyl titanate. All of these conventional ester preparation processes can be carried out using solvents or diluents of the various reactants, if appropriate, and the reaction can be accelerated at elevated temperatures or in the presence of suitable catalysts, such as phase transfer catalysts. Product yield can be increased. The preparation of the individual isomers can be carried out analogously starting from the corresponding individual isomers of the compounds of the formula. Such isomers are obtained from mixtures of isomers by conventional isomer separation methods. For example, cis and trans isomers can be separated by fractional crystallization of a carboxylic acid or its salt, while various optically active forms can be separated by fractional crystallization of a carboxylic acid and an optically active amine, followed by regeneration of the optically pure acid. . The resulting optically pure isomer of the acid (or its acid chloride or ester) can then be reacted with 3-phenoxybenzyl alcohol to produce the final ester compound in individually pure isomeric form. can. In the case of α-cyano-3-phenoxybenzyl alcohol, optically pure α-
Since the reaction of cyano-3-phenoxybenzyl alcohol with a carboxylic acid or its functional derivative cannot be carried out without racemization of the alcohol, a mixture of the two isomers will result.
Typical products of this process include: (±)-α-cyano-3-phenoxybenzyl (1R,3R)-3-(3,3,3-trifluoro-
2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate and (±)-α-cyano-3-phenoxybenzyl (1R,3S)-3-(2- Chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-
Dimethyl cyclopropane carboxylate. These final ester compounds are particularly useful as insecticides. The production of single isomers of these final ester compounds can be achieved by creating an optically pure acid chloride and reacting it with (±)-3-phenoxymandelamide to produce the corresponding (±)-α-carboxyamide ester. This can be achieved by obtaining. These 2
The isomeric esters of the species are separated by fractional crystallization,
Dehydration of individual esters yields the corresponding α-cyano-
It can be 3-phenoxybenzyl ester. It is thus possible to obtain the following single isomers, which are considered to be the most effective insecticidal isomers of the individual compounds: (S)-α-cyano-3-phenoxybenzyl (1R,3R )-3-(3,3,3-trifluoro-
2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate and (S)-α-cyano-3-phenoxybenzyl (1R,3S)-3-(2- Chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-
Dimethyl cyclopropane carboxylate. A preferred group of final ester compounds is such that in the above formula, one of R ¹ and R ² represents the radical WCF ₂ -, where W is hydrogen, fluorine or chlorine, and R ¹
and the other of R ² is a group

A compound represented by the formula: [where X, Y and Z are each hydrogen, fluorine or chlorine] and R ³ represents hydrogen or cyano.
Among this preferred group of compounds, those in which both R ¹ and R ² are trifluoromethyl groups are particularly preferred. Another preferred group of final ester compounds are those in which one of R ¹ and R ² is a group WCF ₂ − (where W
is hydrogen, fluorine or chlorine), the other is fluorine, chlorine or bromine, and R ³ is hydrogen or cyano. In particular, R ¹ and
Preference is given to compounds in which one of R ² represents trifluoromethyl and the other represents chlorine or bromine. The final ester compound may exist in various geometric and stereoisomeric forms. For example, cis and trans isomers resulting from the type of substitution on the cyclopropane ring and E- and Z-isomers resulting from substituted vinyl groups when R ¹ is different from R ² may exist. Additionally, two of the three carbon atoms of cyclopropane are asymmetrically substituted so that they can exist in the R or S configuration, and if R ³ is not hydrogen, the carbon atom to which it is attached can also be in the R or S configuration. It can exist in S configuration. Therefore, in the formula, R ¹ and R ² are the same and R ³
For compounds where is hydrogen, four isomers can exist resulting from substitution of the cyclopropane ring.
These refer to their absolute configuration (1R, 3R),
They can be named (1R, 3S), (1S, 3S) and (1S, 3R). If R ³ is not hydrogen, then 4
Since each of the possible cyclopropane ring configurations of the species exists in two forms corresponding to the S and R configurations of the carbon atom bearing the radical R ³ , eight isomers are possible. Separately, R ³ is hydrogen and R ¹ is R ²
Even when different from . After all, if R ¹ is different from R ² and R ³ is not hydrogen, each compound can exist as 16 isomers. Representative examples of the final ester compounds are shown in Table 1.
Although the compounds shown are racemic mixtures of (+) and (-) isomers, respectively, a distinction is made between cis and trans substitutions on the cyclopropane ring and E and Z substitutions on the vinyl group (if present). . All compounds shown in the table follow the formula:

【table】

【table】

Table: Particularly useful final ester compounds include: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropanecarboxylate, (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-tri Fluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3-chloro −
2,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylate, (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-bromo-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylate; 3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl )-2,2-dimethylcyclopropane carboxylate, and 3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propene-1 -il)-
2,2-dimethylcyclopropane carboxylate. The final ester compounds prepared from compounds of the formula according to the invention can be used for the control of insects and other invertebrate pests, such as mites. Pests that can be controlled using the final ester compounds are used in agriculture (this term includes the cultivation of food and textile crops, horticulture and animal husbandry), forestry and the preservation of plant products such as fruits, grains or timber. Includes related pests and pests associated with the transmission of human and animal diseases. In order to apply the final ester compound to a pest-infested area, the final ester compound is usually used as the insecticidal active ingredient and is further combined with a suitable inert diluent or carrier and/or a suitable inert diluent or carrier.
or formulated into a composition containing a surfactant. Such compositions may further contain another pest control agent,
For example, it may contain other insecticides or acaricides or fungicides, and it may also contain insecticidal synergists such as, for example, dodecylimidazole, safroxan or piperonyl butoxide. The composition may be in the form of a repellent powder in which the active ingredient is mixed with a solid diluent or carrier, such as kaolin, bentonite, diatomaceous earth or talc, or in the form of granules in which the active ingredient is absorbed in a porous particulate material, such as pumice. . The composition can also be used as a liquid for use as a dipping or spraying solution, usually an aqueous dispersion or emulsion containing the active ingredient in the presence of one or more wetting agents, dispersing agents or emulsifying agents (surfactants). It can also be in the form of a formulation. Such agents may be cationic, anionic or nonionic active agents. Suitable cationic activators are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic active agents are soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium, calcium or ammonium lignosulfonate, butylnaphthalene sulfonate and diisopropyl and triisopropyl. Naphthalene is a mixture of sodium salts of sulfonic acid. Suitable nonionic activators are:
It is a condensation product of ethylene oxide and an aliphatic alcohol such as oleyl alcohol or cetyl alcohol or an alkyl phenol such as octylphenol, nonylphenol or octylcresol. Other non-ionic activators are
They are a partial ester derived from a long chain fatty acid and hexitol anhydride, a condensation product of the partial ester and ethylene oxide, and lecithin. The composition comprises dissolving the active ingredient in a suitable solvent, for example a ketone solvent such as diacetone alcohol or an aromatic solvent such as trimethylbenzene;
The resulting mixture can be prepared by adding to water which may contain known wetting agents, dispersing agents or emulsifying agents. Other suitable organic solvents are dimethylformamide, ethylene dichloride, isopropyl alcohol,
Propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylene, trichlorethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA)
It is. A spray composition may also be in the form of an aerosol, in which the formulation is held in a container under pressure in the presence of a propellant, such as fluorotrichloromethane or dichlorodifluoromethane. Compositions used in the form of aqueous dispersions or emulsions are usually supplied in the form of concentrates containing a high proportion of the active ingredient and are diluted with water before use. Such concentrates often need to be capable of withstanding long-term storage and, when diluted with water after such long-term storage, to form an aqueous formulation that remains homogeneous long enough to be applied with conventional spray equipment. It is. Such concentrates may contain from 10 to 85% by weight of active ingredient. When diluted to prepare aqueous formulations, such formulations may contain varying amounts of active ingredient depending on their intended use. Aqueous formulations containing 0.0001 to 0.1% by weight of active ingredient are particularly useful for agricultural and horticultural applications. In use, the composition can be applied using any known method of pesticide application;
It is applied, for example by dusting or spraying, to the pest itself, to the location or habitat of the pest, or to growing plants susceptible to attack by the pest. The final ester compounds and compositions are extremely harmful to a wide range of insects and other invertebrate pests, including the following pests: Aphis fabae, Megoura viceae, Aedes aegypti, Dysdercus fuasciatus. (Dysdercus
Musca domestica Pieris brassicae Plutella maculipennis Phaedon cochleariae Telarius cinnabarinus Aonidiella spp. Whitefly Trialeuroides spp. Blattella germanica) Spodoptera littoralis Vascular terminifefra (Chortiocetes terminifefra) The final ester compounds and compositions containing them are particularly useful for controlling lepidopterous pests of cotton, such as Spodoptera spp. and Heliothis spp. and pests and mites on livestock, such as the sheep fly (Lucilia sericata) and Boophilus spp., Ixodes spp.
spp.), Amblyomma, Rhipicephalus spp. and Dermaceutor spp.). Such compounds and compositions are effective in controlling sensitive and resistant strains of the above pests in adult, larval and intermediate stages and may be applied to host animals infested with the pest by topical, oral or parenteral administration. . Next, examples of manufacturing the compound of the formula according to the present invention, examples of manufacturing the raw materials or intermediate compounds used in the manufacturing, examples of manufacturing the final ester compound having insecticidal activity from the compound of the formula, and insecticidal and sterilizing of the final ester compound are shown. A test example illustrating mite activity is shown. Specifically, Examples 1 to 6 and 10 to 11 are examples of the production of raw materials or intermediate compounds used in the production of the compounds of the present invention, and Examples 16, 19, and 21 are examples of production of the compounds of the present invention having insecticidal activity. Production example of final ester compound, example
Test examples 22 to 25 illustrate the insecticidal and acaricidal activity of the final ester compound, in some cases by comparing it with the activity of known and related compounds, and are for reference only. Example of compound production is Example 7
-9, 12-15, 17, 18 and 20. Example 1 This example describes the preparation of 1-chloro-1,1-difluoro-2-chlorodifluoromethyl-5-methylhexadiene-2,4. (a) Production of 3,3-dimethylallyl triphenylphosphonium bromide 3,3-dimethylallyl bromide (50.0
g), triphenyl phosphine (88.0g) and dry toluene (500ml) was stirred at reflux temperature for 1 hour, heated and then kept at room temperature for 18 hours. Obtained 3,3-dimethylallyl
Triphenylphosphonium bromide (melting point
A white precipitate (242°C) was collected by filtration, washed with diethyl ether, and dried. (b) Production of 1-chloro-1,1-difluoro-2-chlorodifluoromethyl-5-methylhexadiene-2,4 Dry petroleum ether (boiling point range 30-40°C, 500
To a vigorously stirred suspension of 3,3-dimethylallyl triphenylphosphonium bromide (65.0 g) in ml) was added n-butyllithium (65.0 ml of a 15% W/W solution in hexane) at 0°C under nitrogen atmosphere. It was added slowly and the mixture was kept at room temperature for 18 hours. The mixture was then heated to 0°C.
1,3-dichlorotetrafluoroacetone (31.44 g) was added. The resulting mixture was allowed to reach room temperature over 2 hours and the resulting precipitate was separated. The liquid was concentrated by evaporation to a volume of approximately 70 ml and then passed through a short alumina column and the effluent solvent was evaporated at a temperature of 69° C. under atmospheric pressure. The residual liquid was subjected to fractional distillation to collect the fraction with a boiling point of 79-80℃/20mmHg, and then subjected to IR and
It was confirmed to be the title compound by NMR spectrum analysis. NMR ( _CCl4 ): ppm1.88−
1.94 (m, 6H); 6.3 (d, 1H); 7.08 (d, 1H). Example 2 Other diene compounds were prepared from the appropriate ketones by a method similar to Example 1 as follows. (i) 1,1,1-trifluoroacetone to 1,
1,1-trifluoro-2-methyl-5-methylhexadiene-2,4 was produced. NMR ( _CCl4 ): ppm1.76-1.82 (m, 9H);
5.85-6.00 (m, 1H); 6.62-6.78 (m, 1H). (ii) 1,1-difluoro-2-chlorodifluoromethyl-5-methylhexadiene-2,4 was produced from 1-chloro-1,1,3,3-tetrafluoroacetone. IR (liquid film): 3000, 1650, 1265cm ^-1 . (iii) 1,1-difluoro-2-difluoromethyl-5-methylhexadiene-2,4 was produced from 1,1,3,3-tetrafluoroacetone. NMR ( _CCl4 ): ppm1.90-2.02 (m, 6H);
5.65−7.10 (m, 4H). Example 3 This example shows 5-hydroxy-2-methyl-6,6,
The production of 6-trifluoro-5-trifluoromethylhexene-2 will be explained. A stirred mixture of hexafluoroacetone (235g) and 3-methylbutene-1 (100g) was heated at 125°C at 17 atmospheres for 20 hours. The title compound was distilled under reduced pressure with a boiling point of 43℃/15mm.
Obtained as a free flowing colorless liquid of Hg. NMR ( _CCl4 ): ppm1.77 (d, 6H); 2.58-3.00
(m, 3H); 5.0-5.4 (m, 1H). Example 4 From pentafluoroacetone to 5-hydroxy-2-methyl-6,6-
Difluoro-5-trifluoromethylhexene-
2 was manufactured. NMR ( _CCl4 ): ppm1.78 (d, 6H); 2.5-2.75
(m, 3H); 5.18 (m, 1H); 5.80 (t, 1H). Example 5 This example shows the production of ethyl (±)cis/trans-3-(2-hydroxy-3,3,3-trifluoro-2-trifluoromethylpropyl-1)-2,2-dimethylcyclopropane carboxylate. I will explain about it. A solution of ethyl diazoacetate (9.12 g) in dichloromethane (400 ml) was added to 5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhexene-2 (18.9 g) in a catalytic amount. It was added dropwise over 48 hours at 110-120°C in the presence of anhydrous cupric sulfate. The resulting mixture was washed with water, dried over anhydrous magnesium sulfate, and distilled to a boiling point of 68-90℃/0.15mm.
Several fractions in the Hg range were obtained. NMR, IR
and MS spectrum analysis revealed that these fractions were mainly 3-(2-hydroxy-3,3,3-trifluoro-2-trifluoromethylpropyl-
1) -2,2-Dimethylcyclopropane It was found to consist of a mixture of (±)-cis and (±)-trans isomers of ethyl carboxylate in various proportions. NMR ( _CCl3 ): ppm1.04-1.40 (m, 9H); 1.55
−2.43 (m, 4H); 4.00−4.37 (m, 2H). Example 6 By the same method as in Example 5, 5-hydroxy-
2-Methyl-6,6-difluoro-5-trifluoromethylhexene-2 to (±)-cis/trans-3-(2-hydroxy-3,3-difluoro-2-trifluoromethylpropyl-1-yl )
-2,2-dimethyl cyclopropane Converted to ethyl carboxylate. NMR ( _CCl4 ): ppm1.3-2.4 (m, 13H); 4.0-
4.35 (m, 2H); 4.6-4.8 (m, 1H); 5.2-6.4
(m, 1H). Example 7 (Example) This example shows (±)-cis/trans-3(3,3,3
-trifluoro-2-trifluoromethyl-1-
The production of ethyl propen-1-yl)-2,2-dimethylcyclopropane carboxylate will be explained. (±)-cis/trans-3-(2-hydroxy-3,3,3-trifluoro-2-trifluoromethylpropyl-1)-2,2-dimethylcyclopropane ethyl carboxylate (4.62g), oxy A mixture of phosphorous chloride (2.2g) and dry pyridine (5.3ml) was heated at 110°C for 65 hours, then poured into ice water and stirred for 5 hours. The resulting mixture was extracted with diethyl ether, and the extract was washed with water and dried over anhydrous sodium sulfate. After removing the ether by evaporation under reduced pressure, the residual oil was distilled under reduced pressure to give the title compound as a colorless oil with a boiling point of 60-65°C/0.5 mmHg. NMR ( _CDCl3 ): ppm1.15-1.39 (m, 9H); 1.75
-2.60 (m, 2H); 4.02 - 4.34 (m, 2H); 6.36 and 7.36 (dd, 1H). Example 8 (Example) By a method analogous to Example 7, (±)-cis/trans-3-(3,3-difluoro-2-trifluoromethyl-1-propene-1) was prepared from the product of Example 6.
-yl)-2,2-dimethylcyclopropanecarboxylate was obtained. NMR ( _CCl4 ): ppm1.2-1.4 (m, 9H); 1.6-2.6
(m, 2H); 4.0-4.4 (m, 2H); 5.4-7.2 (m,
2H). Example 9 (Example) Following a method similar to Example 5, an ethyl ester of the formula shown below was obtained from the diene compound shown below by reaction with ethyl diazoacetate. (i) 1,1-difluoro-2-difluoromethyl-5-methylhexadiene-2,4 (±)
-cis/trans-3-(3,3-difluoro-2-difluoromethyl-1-propene-1-
yl)-2,2-dimethylcyclopropane ethyl carboxylate. NMR ( _CCl4 ): ppm1.25-1.44 (m, 9H);
1.60-2.40 (m, 2H); 4.0-4.30 (m, 2H);
5.58−7.34 (complex peak, 3H). (ii) 2-trifluoromethyl-5-methylhexadiene-2,4 to (±)-cis/trans-
3-(E/Z-2-trifluoromethyl-1-
Ethyl propen-1-yl)-2,2-dimethylcyclopropane carboxylate. NMR ( _CCl4 ): ppm1.10-1.40 (m, 9H);
1.50-2.10 (m, 5H); 4.0-4.38 (m, 2H);
5.24−6.46 (m, 1H). (iii) 1-chloro-1,1-difluoro-2-chlorodifluoromethyl-5-methylhexadiene-2,4 to (±) cis/trans-3-(3
-Chloro-3,3-difluoro-2-chlorodifluoromethyl-1-propen-1-yl)-
Ethyl 2,2-dimethylcyclopropane carboxylate. NMR ( _CCl4 ): ppm1.28-1.42 (m, 9H);
1.78-2.60 (m, 2H); 4.08-4.26 (m, 2H);
6.20 and 7.16 (dd, 1H). (iv) 1,1-difluoro-2-chlorodifluoromethyl-5-methylhexadiene-2,4 to (±)-cis/trans-3-(E/Z-3,3
-difluoro-2-chlorodifluoromethyl-
Ethyl 1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate. NMR ( _CCl4 ): ppm1.24-1.52 (m, 9H);
1.64-2.50 (m, 2H); 3.90-4.30 (m, 2H);
5.50−7.04 (m, 2H). Example 10 This example shows 3,3-dimethyl-4,6,6-trichloro- with the formula: CF ₃ CCl ₂ CH ₂ CHClC(CH ₃ ) ₂ CH ₂ CO ₂ C ₂ H ₅
The production of ethyl 7,7,7-trifluoroheptanoate is shown. Ethyl 3,3-dimethyl-4-pentenoate (7.0g), 1,1,1-trichloro-2,2,2
- A mixture of trifluoroethane (20.0 g) and benzoyl peroxide (0.1 g) in a closed glass tube.
It was heated at 100°C for 5 hours. The reaction mixture thus obtained was carefully distilled to give 3,3-dimethyl-4,
Ethyl 6,6-trichloro-7,7,7-trifluoroheptanoate was collected as a fraction with a boiling point of 112-114°C/2 mmHg, and this was confirmed by infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy. NMR ( _CDCl3 ) ppm1.13−1.40 (m, 9H), 2.2−
3.0 (m, 4H), 4.07−4.30 (q, 2H), 4.5−4.62
(m, 1H). IR (liquid film) 1728, 1368, 1260, 1180, 1027. Example 11 In the same manner as Example 10, the following haloalkane and 3,
Several halogenated esters were prepared by reacting with ethyl 3-dimethyl-4-heptenoate: (i) 3,3-dimethyl-7,7 from 1,1-difluorotetrachloroethane; -difluoro-
Ethyl 4,6,6,7-tetrachloroheptanoate. NMR ( _CDCl3 ): ppm1.10-1.35 (m, 9H);
2.10−3.00 (m, 4H); 4.12 (q, 2H); 4.52
(dd, 1H) (ii) Ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloroheptanoate from 1,1,2-trifluorotrichloroethane. Product boiling point, 75-76°C/0.05mmHg. (iii) Ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoate from 1,1,1-tribromotrifluoroethane. NMR ( _CDCl3 ): ppm1.16-1.44 (m, 9H);
2.50 (q, 2H); 3.04 (q, 2H); 4.18 (q,
2H); 4.60-4.74 (m, 1H). (iv) 1,1,1-trichloropentafluoropropane to 3,3-dimethyl-7,7,8,
Ethyl 8,8-pentafluoro-4,6,6-trichlorooctanoate. NMR ( _CCl4 ): ppm1.13-1.40 (m, 9H);
2.14−2.92 (m, 4H); 3.96−4.25 (q, 2H);
4.5−4.62 (m, 1H). (v) 1,1,1,3-tetrachlorotetrafluoropropane to 3,3-dimethyl-7,7,
Ethyl 8,8-tetrafluoro-4,6.6,8-tetrachlorooctanoate. NMR ( _CDCl3 ) ppm1.13-1.38 (m, 9H), 2.19
−2.88 (m, 4H), 4.15 (q, 2H), 4.53−4.7
(m, 1H). IR ( _CHCl3 ) 1728, 1476, 1378, 1167, 1103,
1037. Example 12 (Example) This example shows (±)-cis/trans-3-(E/Z-
The production of ethyl 2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate is shown. 3,3-dimethyl-4,6,6 obtained in Example 10
Ethyl trichloro-7,7,7-trifluoroheptanoate was dissolved in anhydrous tetrahydrofuran (30 ml) and this solution was dissolved in sodium t-butoxide (2.75 ml) in anhydrous tetrahydrofuran (120 ml).
g, prepared on the spot from sodium hydride and t-butyl alcohol) at 0°C. After the addition, the mixture was stirred at 0° C. for 2 hours and then acidified with an ethanolic solution of hydrochloric acid. The mixture was diluted with diethyl ether, washed with water, dried over anhydrous magnesium sulfate and concentrated by evaporating the solvent under reduced pressure. The residual yellow oil was carefully distilled under reduced pressure to give (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2 -dimethylcyclopropane ethyl carboxylate (boiling point 70
°C/0.5mmHg). Based on the results of nuclear magnetic resonance analysis, this product contains approximately 60% cis-isomer and approximately 40% cis-isomer.
% of the trans-isomer (with respect to the cyclopropane ring), and in each of the above isomers the trifluoromethyl group is in the trans position with respect to the double bond with respect to the cyclopropane ring. approximately 90-95% are the isomer (Z-isomer) and approximately 5-10% are the isomer in which the trifluoromethyl group is in the cis position with respect to the cyclopropane ring (E-isomer).
It turns out that it exists. NMR ( _CDCl3 ) ppm1.20−1.40 (m, 9H), 1.48−
2.77 (m, 4H), 3.96-4.23 (m, 2H), 6.14,
6.95 (2d, 1H). IR (liquid film) 1722, 1650, 1410, 1378, 1278,
1176, 1140, 950. Example 13 In a similar manner to Example 12, other ethyl esters of the formula were prepared as follows: (i) 3,3-dimethyl-7,7-difluoro-
From ethyl 4,6,6,7-tetrachloropentanoate, (±)-cis/trans-3-(E/Z
-2,3-dichloro-3,3-difluoro-1
-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate. NMR ( _CDCl3 ): ppm1.15-1.55 (m, 9H);
1.55-2.50 (m, 2H); 4.00-4.33 (m, 2H);
6.13 and 6.95 (dd, 1H). (iii) From ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloroheptanoate, (±)-cis/trans-3-(E/Z-
3-chloro-2,3,3-trifluoro-1-
Ethyl propen-1-yl)-2,2-dimethylcyclopropane carboxylate. NMR ( _CCl4 ): ppm1.20-1.58 (m, 9H) 1.58
-2.33 (m, 2H); 4.15 (q, 2H); 5.10,
5.41, 5.91 and 6.25 (4d, 1H). (iii) From ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoate, (±)-cis/trans-3-(2-bromo-3,3,3 Ethyl-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate. NMR ( _CCl4 ): ppm1.10-1.40 (m, 9H);
1.60−2.44 (m, 2H); 3.96−4.28 (m, 2H);
5.96−7.26 (m, 1H). (iv) From ethyl 3,3-dimethyl-7,7,8,8,8-pentafluoro-4,6,6-trichlorooctanoate, (±)-cis/trans-3-
Ethyl (2-chloro-3,3,4,4,4-pentafluoro-1-buten-1-yl)-2,2-dimethylcyclopropanecarboxylate. NMR (CCl ₄ ): ppm1.15−2.53 (complex peaks,
11H); 3.92-4.30 (m, 2H); 6.12 and 6.92
(dd, 1H). (v) From ethyl 3,3-dimethyl-7,7,8,8-tetrafluoro-4,6,6,8-tetrachlorooctanoate, (±)-cis/trans-3
-(2,4-dichloro-3,3,4,4-tetrafluoro-1-buten-1-yl)-2,2
-Ethyl dimethylcyclopropanecarboxylate. NMR (CCl ₄ ) ppm 1.20−1.41 (m, 9H), 1.62−
2.48 (m, 2H), 3.95-4.24 (m, 2H), 6.10,
6.88 (2d, 1H). IR (liquid film) 1725, 1650, 1224, 1137, 1075. Example 14 (Example) This example shows (±)-cis/trans-3-(3,3,
3-trifluoro-2-trifluoromethyl-1
-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. (±)-Ethyl cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (0.52 g), Glacial acetic acid (2.52
ml), hydrobromic acid (48 W/V%, 3.36 ml) and water (1.12 ml) was heated at reflux temperature for 10 hours. After cooling the reaction mixture, it was diluted with water (50 ml) and extracted several times with diethyl ether.
The extracts were combined, washed with water, dried over anhydrous sodium sulfate and then concentrated by evaporating the ether under reduced pressure. Based on the results of spectral analysis, the residual oil is mainly (±)-cis/trans-3-(3,
It was found to consist of 3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. NMR (CCl ₄ ) ppm 1.27−1.47 (m, 6H), 1.60−
2.67 (m, 2H), 6.36−7.25 (2d, 1H). IR (liquid film) 3450−2400, 1705, 1670, 1455,
1380, 1055. Example 15 (Example) This example shows (±)-cis/trans-3-(3,3,
3-trifluoro-2-trifluoromethyl-1
Figure 2 shows the conversion of -propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid to acid chloride. (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid (0.4 g) and chloride Thionyl (5.0
ml) was heated at reflux temperature for 2 hours, excess thionyl chloride was removed by vacuum distillation,
(±)-cis/trans-1-chlorocarbonyl-
3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)2,2-
Dimethylcyclopropane was obtained. Example 16 This example shows (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,
3-trifluoro-2-trifluoromethyl-1
-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (hereinafter compound No. 1)
The following describes the production of (±)-cis/trans-1-chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,
Residues consisting of 2-dimethylcyclopropane (e.g.
15), pyridine (0.12 g) and (±)-α-
A mixture of cyano-3-phenoxybenzyl alcohol (0.33 g) was added and the resulting mixture was stirred at ambient temperature for 16 hours. After adding water (20 ml), extraction was carried out with diethyl ether (10
ml x 3 times). After combining the extracts and washing successively with water, saturated aqueous sodium carbonate solution and water,
Dry over anhydrous sodium sulfate. After removing the ether by vacuum distillation, the residual oil was subjected to preparative thick-layer chromatography using 2 mm thick silica on glass and chloroform as eluent to yield approximately 20% cis-isomers and approximately 80% cis-isomers. Trans-
(±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3 containing isomers
-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-
Dimethyl cyclopropane carboxylate (Rf0.53) was obtained. Spectral analysis: Infrared spectrum: 1755, 1680, 1600, 1490,
1300, 1160 NMR: 0.9−2.5τ, 6.0−6.15τ, 6.35−7.2τ Mass spectra: M ⁺ 483 (275, 259, 231,
209, 208, 181) Example 17 (Example) This example shows (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropanecarboxylic acid. (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropanecarboxylate (0.52 g), glacial acetic acid (2.52 ml), hydrobromic acid (48 W/V%, 3.36 ml) and water (1.12 ml)
The mixture was heated at reflux temperature for 10 hours. After cooling the reaction mixture, it was diluted with water (50 ml) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and then concentrated by evaporating the ether under reduced pressure. Based on the results of spectral analysis, the residual oil is mainly (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropanecarboxylic acid. NMR ( _CDCl3 ) ppm1.20−1.46 (m, 6H), 1.67−
2.63 (m, 2H), 6.17, 6.88 (2d, 1H). IR (liquid film) 3400−2200, 1693, 1650, 1350,
1280, 1190, 1125. Example 18 (Example) This example shows (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane. 1 shows the conversion of a carboxylic acid to an acid chloride. (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
After heating a mixture of 2,2-dimethylcyclopropanecarboxylic acid (0.4 g) and thionyl chloride (5.0 ml) at reflux temperature for 2 hours, excess thionyl chloride was removed by vacuum distillation to give (±) -cis/trans-1-chlorocarbonyl-3-(2-chloro-3,3,3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropane was obtained. NMR ( _CDCl3 ) ppm1.32-143 (m, 6H), 2.24-
2.68 (m, 2H), 5.84-6.72 (m, 1H). IR (liquid film) 1777, 1650, 1380, 1275, 1140, 980. Example 19 This example shows (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as compound No. 6)
The production of is shown. A residue consisting of (±)-cis/trans-1-chlorocarbonyl-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane ( (see example 18)
, pyridine (0.12 g) and (±)-α-cyano-
A mixture of 3-phenoxybenzyl alcohol (0.33g) was added and the resulting mixture was stirred at ambient temperature for 16 hours. After adding water (20 ml), extraction was performed with diethyl ether (10 ml x 3).
The extracts were combined, washed successively with water, saturated aqueous sodium carbonate solution, and water, and then dried over anhydrous sodium sulfate. After removing the ether by vacuum distillation, the residual oil was subjected to preparative thick layer chromatography using 2 mm thick silica on glass and chloroform as eluent to give (±)-α-cyano-3-phenoxy Benzyl (±)-cis-3
-(2-chloro-3,3,3-trifluoro-1
-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (Rf 0.52) and the corresponding trans isomer (Rf 0.42) were obtained. Each of the above isomers contained about 90-95% of the Z-isomer. Spectral analysis: Infrared spectrum (CHCl ₃ )
1740, 1660, 1590, 1480, 1460cm ^-1 ; NMR
( _CCl4 ): 6.90−7.50τ, 1.60−2.70τ, 1.50−
1.00τ and a special peak, 6.3τ (benzylic H), are believed to be assigned to Z-cis, E-cis, Z-trans and E-trans, respectively. 6.85, 6.50, 6.11 and 5.84τ (Vinyl H) Example 20 The following carboxylic acids were prepared from the corresponding ethyl esters by using methods similar to those described in Examples 14 and 17. (i) (±)-cis/trans-3-(3,3-difluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR (liquid film): 3500~2400, 1700, 1665cm ^-1 . (ii) (±)-cis/trans-3-(3,3-difluoro-2-difluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.30-1.50 (m, 6H);
1.70-2.60 (complex peak, 2H); 5.70-7.13
(complex peak, 3H). (iii) (±)-cis/trans-3-(E/Z-2-
Trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.22-1.44 (m, 6H); 1.6
~2.3 (m, 5H); 5.36 ~ 6.6 (m, 1H); 11.9
(S, 1H). (iv) (±)-cis/trans-3-(3-chloro-
3,3-difluoro-2-chlorodifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.24-1.42 (m, 6H);
1.80-2.68 (m, 2H); 6.16 and 7.12 (dd,
1H); 11.6 (S, 1H). (v) (±)-cis/trans-3-(E/Z-3,
3-difluoro-2-chlorodifluoro-methyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR ( _CHCl3 ): 3450~2500, 1705, 1675 ^cm-1 . (vi) (±)-cis/trans-3-(2-bromo-
3,3,3-trifluoro-1-propene-1
-yl)-2,2-dimethylcyclopropane
carboxylic acid. IR ( _CHCl3 ): 3400~2450, 1700, 1650, 1275,
1140cm ^-1 . (vii) (±)-cis/trans-3-(3-chloro-
2,3,3-trifluoro-1-propene-1
-yl)-2,2-dimethylcyclopropane
carboxylic acid. IR (oil film): 3400~2200, 1700, 1450, 1140,
1070 ^-1 . (viii) (±)-cis/trans-3-(2,3-dichloro-3,3-difluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylic acid. IR ( _CHCl3 ): 3400~2200, 1700cm ^-1 . (ix) Pure (±)-cis-3-(2,3-dichloro-3,3-difluoro-1-propen-1-yl)- on cooling from a concentrated solution of mixed cis and trans acids in hexane. 2,2-dimethylcyclopropane carboxylic acid precipitates. NMR ( _CDCl3 ): ppm1.25 (S, 6H); 1.80~
2.25 (m, 2H); 6.73 (d, 1H). (x) (±)-cis/trans-3-(2-chloro-
3,3,4,4,4-pentafluoro-1-buten-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. NMR ( _CDCl3 ): ppm1.10-1.50 (m, 6H);
1.68-2.58 (m, 2H); 6.14 and 6.85 (dd,
1H). () (±)-cis/trans-3-(2,4-
dichloro-3,3,4,4-tetrafluoro-
1-Buten-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR (CCl ₄ ) ppm 1.20−1.49 (m, 6H), 1.72−
2.56 (m, 2H), 6.15, 6.87 (2d, 1H). IR ( _CHCl3 ) 3500−2400, 1705, 1160, 1100. Example 21 3-Phenoxybenzyl alcohol, (±)-α
-Cyano-3-phenoxybenzyl alcohol or (±)-α-ethynyl-3-phenoxybenzyl alcohol by reacting acid chloride with the various carboxylic acids of Example 20 to form a final product with insecticidal activity. Convert to ester compound. These reaction products (hereinafter referred to as products Nos. 2-5 and 7-29) are mostly mixtures of two or more of the compounds in Table 1, as shown below. Product No. 2: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2
-dimethylcyclopropane carboxylate, which is a mixture of 1 part of Compound No. 1 and 1 part of Compound No. 2. NMR ( _CCl4 ): ppm1.20-1.40 (m, 6H);
1.80~2.30 (m, 2H); 6.17~6.37 and 6.85~
7.42 (mm, 11H). Product No. 3: (±)-α-cyano-3-phenoxybenzyl (±)-trans-3-(3,3,
3-trifluoro-2-trifluoromethyl-
1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate, which is Compound No. 2 alone. NMR (CCl ₄ ) ppm 1.07−1.40 (m, 6H), 1.75−
2.50 (m, 2H), 6.0, 7.28 (m, 11H). Product No. 4: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(3,3,3-
Trifluoro-2-trifluoromethyl-1-
propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a compound
No.1 alone. NMR (CCl ₄ ) ppm 1.14−1.40 (m, 6H), 1.80−
2.25 (m, 2H), 6.04-7.27 (m, 11H). Product No. 5: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(2-chloro-
3,3,3-trifluoro-1-propene-1
-yl)-2,2-dimethylcyclopropane
Carboxylate, which is a mixture of 19 parts of Compound No. 31 and 1 part of Compound No. 32. Product No. 7: 3-phenoxybenzyl (±)-
cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is compound no.
It is a mixture of 11 parts and 14 parts of Compound No. 4. NMR ( _CCl4 ): ppm1.18-1.40 (m, 6H);
1.75-2.55 (m, 2H); 5.15 (s, 2H); 6.30 and 6.70-7.40 (dm, 10H). Product No. 8: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(3,3-difluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of compounds Nos 15, 16, 17 and 18 (composition not determined). ). IR (liquid film): 1745, 1655, 1595cm ^-1 . Product No.9: 3-phenoxybenzyl (±)-
cis/trans-3-(Z-2,3-dichloro-3,3-difluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate, which is part of compound no. It is a mixture with a part of Compound No. 41. NMR ( _CDCl3 ): ppm1.20-1.37 (m, 6H);
1.73-2.50 (m, 2H); 5.10 (d, 2H); 6.12 and 6.88-7.48 (dm, 10H). Product No. 10: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(Z/E-2,3-dichloro-3,3-difluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is 19 parts of compound No. 43 and compound no. 1 part of Compound No. 44, 19 parts of Compound No. 45, and 1 part of Compound No. 46
It is a mixture with parts. NMR ( _CCl4 ): ppm1.18-1.45 (m, 6H);
1.73-2.50 (m, 2H); 6.32 (m, 1H); 6.08 and
6.81 (dd, 1H); 6.90-7.44 (m, 9H). Product No. 11: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(Z/E-2,
3-dichloro-3,3-difluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a compound
It is a mixture of 19 parts of No. 43 and 1 part of Compound No. 44. NMR ( _CCl4 ): ppm1.18-1.40 (m, 6H);
1.92-2.32 (m, 2H); 6.31 (d, 1H); 6.81
(d, 1H); 6.90-7.45 (m, 9H). Product No. 12: 3-phenoxybenzyl (±)
-cis-3-(Z/E-2,3-dichloro-3,
3-difluoro-1-propen-1-yl)-
2,2-dimethylcyclopropanecarboxylate, which consists of 19 parts of compound No. 39 and the compound
It is a mixture with one part of No.40. NMR ( _CCl4 ): ppm1.05-1.48 (m, 6H);
1.84~2.38 (m, 2H); 5.02 (s, 2H); 6.72~
7.45 (m, 10H). Product No. 13: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(Z/E-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a compound
1 part of No. 19, 9 parts of compound No. 20, and the compound
It is a mixture of 1 part of Compound No. 21 and 9 parts of Compound No. 22. NMR ( _CCl4 ): ppm1.22-1.40 (m, 6H);
1.60-2.30 (m, 5H); 5.2-6.45 (m, 1H). Product No. 14: 3-phenoxybenzyl (±)
-cis/trans-3-(Z/E-2-trifluoromethyl-1-propen-1-yl)-2,
2-dimethylcyclopropane carboxylate, which is part of compound No. 23 and compound
9 parts of No. 24, 1 part of compound No. 25 and the compound
It is a mixture with 9 parts of No.26. NMR ( _CCl4 ): ppm1.22-1.40 (m, 6H);
1.58~2.2 (m, 5H); 5.02 (s, 2H); 5.2~
6.45 (m, 1H); 6.85-7.42 (m, 9H). Product No. 15: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(Z
-3-chloro-2,3,3-trifluoro-1
-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of one part of Compound No. 47 and one part of Compound No. 48. NMR ( _CCl4 ): ppm1.15-1.40 (m, 6H);
1.65-2.40 (m, 2H); 5.08, 5.39, 5.80 and
6.12 (4d, 1H); 6.35 (m, 1H); 6.92-7.50
(m, 9H). Product No. 16: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(Z-3-chloro-2,3,3-trifluoro-1-propene-1- yl)-2,2-dimethylcyclopropane carboxylate, which is Compound No. 47. NMR ( _CCl4 ): ppm1.18-1.40 (m, 6H);
1.85-2.33 (m, 2H); 5.80 and 6.11 (dd,
1H); 6.35 (d, 1H); 6.95-7.60 (m, 9H). Product No. 17: 3-phenoxybenzyl (±)
-cis/trans-3-(Z-3-chloro-2,
3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate, which is a mixture of one part of Compound No. 49 and one part of Compound No. 50. NMR ( _CCl4 ): ppm1.15-1.30 (m, 6H);
1.65-2.40 (m, 2H); 5.10, 5.40, 5.92 and
6.23 (m, 3d, 3H); 6.90-7.45 (m, 9H). Product No. 18: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2
-dimethylcyclopropane carboxylate, which is a mixture of 1 part of Compound No. 1 and 2 parts of Compound No. 2. Product No.19: 3-phenoxybenzyl (±)
-cis/trans-3-(3,3-difluoro-2-difluoromethyl-1-propene-1-
yl)-2,2-dimethylcyclopropanecarboxylate, which is a mixture of 3 parts of Compound No. 5 and 2 parts of Compound No. 6. NMR ( _CCl4 ): ppm1.18-1.37 (m, 6H);
1.60-2.45 (m, 2H); 5.03-5.1 (m, 2H);
5.13-7.47 (complex peak, 12H). Product No. 20: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(3,3-difluoro-2-difluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a combination of 3 parts of compound No. 7 and 2 parts of compound No. 8. It is a mixture. NMR ( _CCl4 ): ppm1.20-1.40 (m, 6H);
1.80~2.47 (m, 2H); 6.17~6.37 and 6.85~
7.43 (mm, 13H). Product No. 21: 3-phenoxybenzyl (±)
-cis/trans-3-(Z/E-2-chloro-3,3,3-trifluoro-1-propene-
1-yl)2,2-dimethylcyclopropane
Carboxylate, which is a mixture of 9 parts of Compound No. 35, 1 part of Compound No. 36, 6 parts of Compound No. 37, and 4 parts of Compound No. 38. Product No. 22: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3(Z-
2,4-dichloro-3,3,4,4-tetrafluoro-1-buten-1-yl)-2,2-dimethylcyclopropane carboxylate, which is 9 parts of compound No. 51 and compound No. 52 It is a mixture with one part of. Product No. 23: (±)-α-cyano-3-phenoxybenzyl (±)-trans-3-(Z-2-
Chloro-3,3,4,4,4-pentafluoro-1-buten-1-yl)-2,2-dimethylcyclopropane carboxylate, which is Compound No. 53. NMR ( _CCl4 ): ppm1.16-1.42 (m, 6H);
1.74~2.60 (m, 2H); 5.98~6.40 and 6.77~
7.55 (mm, 11H). Product No. 24: 3-phenoxybenzyl (±)
-cis/trans-3-(3-chloro-3,3
-difluoro-2-chlorodifluoromethyl-
1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of 7 parts of Compound No. 9 and 13 parts of Compound No. 10. NMR ( _CCl4 ): ppm1.24-1.42 (m, 6H);
1.76-2.60 (m, 2H); 5.02 (s, 2H); 6.16 and 7.12 (dd, 1H), 6.76-7.40 (m, 9H). Product No. 25: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3
-Chloro-3,3-difluoro-2-chloro-
difluoromethyl-1-propen-1-yl)
-2,2-dimethylcyclopropane carboxylate, which consists of 7 parts of compound No. 11 and the compound
It is a mixture with 13 parts of No.12. NMR ( _CCl4 ): ppm1.24-1.42 (m, 6H);
1.84-2.70 (m, 2H); 6.16 and 7.12 (dd,
1H); 6.36 (ss, 1H); 6.90-7.50 (m, 9H). Product No. 26: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-
(Z/E-3,3-difluoro-2-chloro-
difluoromethyl-1-propen-1-yl)
-2,2-dimethylcyclopropane carboxylate, which is compound No. 27, 28, 29 and 30
It is a mixture of undetermined composition containing . NMR ( _CCl4 ): ppm1.24-1.52 (m, 6H);
1.76-2.70 (m, 2H); 5.6-7.6 (m, 12H). Product No. 27: (±)-α-cyano-3-phenoxydinyl (±)-cis/trans-3(Z/
E-2-bromo-3,3,3-trifluoro-
1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is 10 parts of compound No. 54 and 1 part of compound No. 55,
It is a mixture of 10 parts of Compound No. 56 and 1 part of Compound No. 57. NMR ( _CCl4 ): ppm1.24-1.50 (m, 6H);
1.75-2.55 (m, 2H); 5.96-7.26 (m, 1H);
6.36-6.56 (m, 1H); 7.0-7.6 (m, 9H). Product No. 28: (±)-α-ethynyl-3-phenoxybenzyl (±)-cis/trans-3-
(Z/E-2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which consists of 10 parts of compound No. 58 and compound no. .59 no 1
1 part of Compound No. 60, and 1 part of Compound No. 61. NMR ( _CCl4 ): ppm1.16-1.44 (m, 6H);
1.64-2.56 (m, 3H); 5.7-7.0 (m, 1H);
6.28-6.40 (m, 1H); 6.70-7.40 (m, 9H). Product No. 29: (±)-α-ethynyl-3-phenoxybenzyl (±)-cis/trans-3-
(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2
-dimethylcyclopropane carboxylate, which is 2 parts of compound No. 13 and 2 parts of compound No. 14
It is a mixture with 3 parts of NMR ( _CCl4 ): ppm1.16-1.44 (m, 6H);
1.76-2.56 (m, 3H); 6.12-7.04 (m, 1H);
6.24-6.40 (m, 1H); 6.76-7.36 (m, 9H). Example 22 This example uses (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-3,3,3 -trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2
-dimethylcyclopropane carboxylate (containing 60% cis isomer - product no. 6) and (±)-α-cyano-3-phenoxybenzyl
(±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate (cis isomer Including %-
This is to explain the insecticidal activity of product No. 1). The activity of the above products was tested against various insects and other invertebrate pests. Each product is a product
In the case of No. 1, this is 1000, 500,
125 and 62.5 ppm, and in the case of product No. 6 it was used in the form of a liquid formulation containing 50, 25, 12.5 and 6.25 ppm. These formulations involve dissolving each compound in a solvent mixture consisting of 4 volumes of acetone and 1 volume of diacetone alcohol, and then combining the solution with a wetting agent sold under the trade name "Lisapol" NX.
It was prepared by diluting with water containing 0.01% by weight until a liquid formulation containing the required concentration of active compound was obtained. The test method employed for each test pest was essentially the same, consisting of supporting a large number of pests on a medium, usually the host plant or some type of food for which it feeds. or both, consisting of treatment with the test formulation. Mortality of the pests was then evaluated at appropriate times, 1-3 days after treatment. The test results are shown in Tables 1 and 2. In these tables, the first column indicates the species and common name of the pest tested, and the following columns indicate the host plant or medium that supported the pest, the number of days elapsed after treatment and before assessment of pest mortality, and the following columns indicate the species and common name of the pest tested. The results obtained for each concentration of test compound are shown. The evaluation is expressed by the following numerical value from 0 to 3. 0 Killing rate 30% or less 1 Killing rate 30-49% 2 Killing rate 50-90% 3 Killing rate 90% or more In the table, a dash (-) indicates that the test was not conducted. A "contact test" indicates that both pest and media were treated, and a "residue test" indicates that the media was treated before infesting the media with pests. The results for Product No. 1 are shown in Table 1, and the results for Product No. 6 are shown in Table 1.

【table】

【table】

Table: Example 23 This example illustrates the insecticidal activity of the product of Example 21. The test was conducted under the same conditions as Example 22. The test results are shown in the table as % pest mortality at a single application rate for each product. The application rate is expressed as the ppm concentration of the active ingredient in the test formulation. The symbols used for the test pests in the table have the following meanings: “A” - Tetranychus telarius (red spider mite, adult) “B” - Tetranychus telarius (red spider mite, eggs) “C” - Aphis fabae (black aphid) ) "D" - Megoura viceae (green aphid) "E" - Aedes aegypti (mosquito) "F" - Musca domestica (house fly - contact activity) "G" - Musca domestica (house fly - residual activity) "H" - Plutella xylostella (residual activity 3 days) “I” - Plutella xylostella (residual activity 10 days) “J” - Phaedon cochleariae (mustard beetle) “K” - Calandra qranaria (white beetle) “L” - Tribolium castaheum (flour beetle) “M” - Spodoptora littoralis (Spodoptora littoralis) The asterisk (*) in the table indicates that in addition to the indicated mortality rate, surviving pests were also severely affected and would have died if the test period was extended. means.

【table】

[Table] Example 24 This example describes the acaricidal activity of products No. 2 and No. 6 against cattle ticks (Boophilus microplus). 10 parts of each product with 985 parts of water and “Teric”N9
(“Teric” is a registered trademark and “Teric” N9 is a nonionic surfactant obtained by condensing nonylphenol and ethylene oxide in a molar ratio of 1:9). A suspension containing 1.0% of the active ingredient was prepared. A portion of this suspension is diluted with water to give 0.1% active ingredient.
A composition containing 0.01% and 0.01% was obtained. The efficacy of each test product against adult (female) ticks of the strain "Yeerongpilly" was tested by applying a small amount of the suspension to each of about 20 ticks. After 14 days, adult tick mortality was assessed by calculating the number of eggs laid and the percentage of hatched eggs. The results are shown in Table 1. The efficacy of each test product against mite larvae of the "Yeerongpilly" strain was tested as follows. The paper was immersed in a suspension of the above concentration and then dried, the treated paper was shaped into a wrapper, and about 100 larvae of the above mite were wrapped in the wrapper. The mortality rate of mite larvae was calculated 48 hours after packaging, and the kill rate was expressed on a scale of 0 to 5: 0 Kill rate 0-20% 1 〃 20-50% 2 〃 50-80% 3 〃 80-95% 4 〃 95-99% 5 〃 100% The results are shown in the table. In another test, 25 parts of the test compound were mixed with 75 parts of cyclohexanone and 25 parts of "Teric"N9;
Emulsions of each test product were prepared by diluting this mixture with water to give 10,000 parts by volume of emulsion. The emulsion thus obtained was sprayed in drops onto calves infested with cattle ticks of the resistant "Biana" strain at various stages of growth. The efficacy of each test product was evaluated as follows. (i) All adult mites (female) that were fully mature at the time of spraying were collected immediately after spraying and placed in a Petri dish in an incubator, and the mortality rate was calculated as egg production capacity and surviving larvae if eggs were laid. Evaluation was based on egg viability as indicated by hatching. Mature adults (if present) were similarly collected 24 and 48 hours after spraying to assess mortality. This assessment is based on “mortality – engorged adults.”
The results are shown in Table 1. (ii) Every other day, scheduled sampling areas on each calf were examined for the effect of the active ingredient on immature adults and nymphs. This evaluation is expressed on the scale 0 to 5 described above and is referred to as "mortality rate - immature adults" and "mortality rate - nymphs." The results are shown in Table 1. In the table, the symbol "-" indicates that there were no mature adults. In these tests, permethrin, i.e. 3-phenoxybenzyl (±)-
cis/trans-3(2,2-dichlorovinyl)-
2,2-dimethylcyclopropanecarboxylate was used.

【table】

[Table] Example 25 Representative compounds of the present invention, namely 3-(2-
Chloro-3,3,3-trifluoroprop-1-
3-phenoxybenzyl ester (compound A) derived from en-1-yl)-2,2-dimethylcyclopropanecarboxylic acid and α-cyano-3-
The insecticidal activity of phenoxybenzyl ester (compound B) was evaluated using an example of 3-phenoxybenzyl ester of the target compound (R ₄ =H) of the general formula () disclosed in JP-A-51-131857. Some 3-(2,
3-dichlorobut-1-en-1-yl)-2,
In order to compare the insecticidal activity of 3-phenoxybenzyl ester of 2-dimethylcyclopropanecarboxylic acid (comparative compound), each test compound was applied to the pests shown in the latter table at concentrations of 10, 5, and 1 ppm. The mortality rate (%) was calculated and the results are shown in the table below.

[Table] The above test results show that the comparative compounds have extremely limited insecticidal activity, whereas insecticidal compounds A and B derived from the compounds of the present invention have high insecticidal activity against a wider range of insect pests. It shows that it has.

Claims (1)

[Claims] Primary formula: [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or a group (where X, Y and Z each represent hydrogen, fluorine or chlorine); Q represents a hydroxy group, a lower alkoxy group containing up to 6 carbon atoms or a chlorine atom; ] A cyclopropane derivative represented by 2 In the formula, one of R ¹ and R ² is a group WCF ₂
- (wherein W is hydrogen, fluorine or chlorine), the other of R ¹ and R ² represents a group [formula] (wherein X, Y and Z each represent hydrogen, fluorine or chlorine), 2. A compound according to claim 1, wherein Q represents a hydroxy group, a lower alkoxy group containing 1 to 3 carbon atoms, or a chlorine atom. 3 One of R ¹ and R ² represents a group WCF ₂ - (where W is hydrogen, fluorine or chlorine), the other represents fluorine chlorine or bromine, Q is a hydroxy group, 1-
2. A compound according to claim 1, which represents a lower alkoxy group containing 3 carbon atoms or a chlorine atom. 4. The compound according to claim 1 or 2, wherein R ¹ and R ² are both trifluoromethyl groups. 5. The compound according to claim 1 or 3, wherein one of R ¹ and R ² represents a trifluoromethyl group and the other represents chlorine or bromine. 6 The following compound: (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylic acid; (±)-cis/trans-3-(2-bromo-
3,3,3-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid; (±)-cis/trans-3-(3,3,3-trifluoro-2 -trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid; and (±)-cis/trans-3-(3-chloro-
2,3,3-trifluoro-1-propene-1-
2,2-dimethylcyclopropane carboxylic acid; 7. A compound according to claim 6 in the form of an ethyl ester. 8th formula: The following formula consists of reacting a diene compound of (wherein R ¹ and R ² have the meanings given below) with a lower alkyl ester of diazoacetic acid; [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or a cyclo group of the formula (where X, Y and Z represent hydrogen, fluorine or chlorine respectively) and Q ¹ represents a lower alkoxy group containing up to 6 carbon atoms; Method for producing propane derivatives. 9. The production method according to claim 8, wherein the lower alkyl ester of diazoacetic acid is ethyl diazoacetate. 10. The manufacturing method according to claim 8 or 9, wherein the diene compound is used in an excess amount. 11. The production method according to any one of claims 8 to 10, wherein the reaction is carried out in the presence of a metal catalyst. 12 Next step: (a) The following formula: (wherein R ¹ ' and R ² ' have the meanings given below) is treated with a lower alkyl ester of diazoacetic acid; and (b) the following formula is thus formed: (wherein R ¹ ′, R ² ′ and Q ¹ have the meanings given below) is dehydrated using a chemical dehydrating agent; (In the formula, R ¹ ' and R ² ' are both trifluoromethyl groups, or one of R ¹ ' and R ² ' is a trifluoromethyl group and the other is a difluoromethyl group, and Q ¹ is 6 A method for producing a cyclopropane derivative represented by a lower alkoxy group containing up to 1 carbon atoms. 13. The manufacturing method according to claim 12, wherein the chemical dehydrating agent is phosphorus pentoxide. 14th formula: (In the formula, R ¹ , R ² and Q ¹ have the meanings given below,
W' and W'' represent fluorine, chlorine or bromine, respectively, provided that when R ² is bromine, W' shall represent bromine) with at least 2 molar equivalents of chlorine. The following equation consists of: [In the formula, one of R ¹ and R ² represents a group W-(CF ₂ ) _n - (where W is hydrogen, fluorine or chlorine, and m is 1 or 2), and R ¹ and R ² The other is fluorine,
chlorine, bromine or a cyclo group of the formula (where X, Y and Z represent hydrogen, fluorine or chlorine respectively) and Q ¹ represents a lower alkoxy group containing up to 6 carbon atoms; Method for producing propane derivatives. 15 Claim 1 in which the base is an alkali metal lower alkoxide containing up to 6 carbon atoms
The manufacturing method described in Section 4.